Transition metal catalyzed cooligomerizations of alpha, omega-diynes with monoacetylenes, nitriles, and alkenes will be explored as crucial steps in the synthesis of molecules of physiological interest. Our recent synthesis of steroids based on this methodology will be extended to the synthesis of novel steroid derivatives. Stoichiometric reactions of appropriate acyclic precursors with transition metal complexes to give polycyclic ligands with control of stereochemistry will be explored. A general synthesis of the isoquinoline nucleus based on the acetylene cyclization principle, will be extended to the synthesis of quinoline derivatives. The use of stannyl acetylenes in these cyclizations will be explored.